Thermodynamics of a compressible lattice gas crystal: Generalized Gibbs-Duhem equation and adsorption

Abstract: Compressible lattice gas models are used in material science to understand the coupling between composition and strain in alloys. The seminal work in this field is the 1973 Larch\'{e}-Cahn paper (Acta Metall. {\bf 21} 1051-1063). Single-phase crystals in Larch\'{e}-Cahn theory are stable under open constant pressure, constant temperature conditions. The Gibbs free energy does not have to match the product $\mu N$ of the number of particles $N$ and their chemical potential $\mu$. Discrepancies already arise under hydrostatic stress. The reason is that volume strain is defined with respect to a fixed reference state. The elastic energy is not proportional to volume and the Gibbs-Duhem relation valid for liquids is violated. Extensivity can be recovered by treating the number of lattice sites $M$ as an additional thermodynamic variable. This assigns a formal chemical potential $\nu$ to the immobile lattice sites. The difference $ G-\mu N $ can be identified with $\nu M$. We have worked this out for a one-component compressible lattice gas crystal. Shear stress is omitted. The reinstated Gibbs-Duhem equation can be cast in the form of an adsorption equation and applied to quantify the tendency to vacancy creation. The derivative of population with respect to chemical potential at constant pressure and temperature is compared to the corresponding susceptibility in a fixed volume open system. We find that the difference is proportional to the elastic constant of the bare lattice, confirming that this quantity is the crucial macroscopic property distinguishing a solid under hydrostatic stress from a liquid.